N-heterocyclic substituted guanamines



Patented June 21, 1949 UNITED srATs OFFICE N -HETEROCYCLIC SUBSTITUTEDGUANAMINES Jack Theo Thurston, Cos Cob, Conn., assignor to AmericanCyanamid Company, New York, N. Y., a corporation of Maine No Drawing.Application August 30, 1941, Serial No. 409,153

1 Claim. (Cl. 260-2495) 1 2 This invention relates to N-Heterocyclicguanatail in conjunction with the following specific mines. examples.The parts are by weight.

Guanamines of the present invention may be represented by the formula: 5M E 1 R 4-N-2'- (4'-methyl) -thiaz0lyl hexanoguanamine 7 051111 x\ N% lll' /z ('1 N "J d-N 10 N \N 11 lfil'(| |l-CH; v N v mN-t: (Lit-c 0-Hwhere R. is hydrogen, alkyl, aryl or heterocyclic,

x is a heterocyclic grou and y is hydrogen, alkyl, aryl or heterocyclic.Guanamines pro-- 15 duced according to the present invention are capableof reacting with formaldehyde to yield resins which in some cases arethermoplastic and in others thermosetting. The guanamines can also beused for the manufacture of drugs, corrosion inhibitors, and the like.

The present invention is not limited to any particular method ofpreparing the guanamines. Two methods, however, appear to give the besta carboxylic acid if desired in the presence of a 2 2 condensing agentsuch as a metal alkoxide. The EXAMPLE 2 second method consists of fusingthe unsubstituted guanamines with a salt of the desired 'mmdylformoguanamme heterocyclic amine. The reaction is preferably H Hefi'ected in the presence of a solvent which makes 5 5 the mix morefluid and reduces losses due to sublimation when reflux equipment isused. N N HO OH Various fluxes may be used but phenol is cheap L J andefficient and is a preferred material. Amine salts such as the followingmay be used in the N iu tlituiit fitinititii teiifiycit iifiifiitf gg -f53%; ,5 f 3 aminoquinoline (also 4, 5, or G-aminoquinoline), 23 m i irfi ir i 15; gi of m t haiidl.

3'ammocarbazole 2ammoacndme After stirring at room temperature for twohours,

methwisoxazole f h the mixture was refluxed for fifteen minutes, the 2-ammophenylth1azme, furiurylamine, difurfur- Sadium sulfate was removedby filtration, and

T 3'ammof5methyl'L2Atnazole and after cooling to room temperature 9parts of ammoacetoguajnamma 4 methyl formate were added. After standingfor When reaction with an ester is employed 1t about two hours, tguanamine precipitated is preferable to carry out the react1n m a fromsolution, and after filtration it was dissolvent Among 9 eff ect1Vesolvents are solved in hydrochloric acid, and reprecipitated the lowermonohydric aliphatic alcohols, such as with dilute ammonium hydroxideThe product methanol, ethanol, the ethyl ether of ethylene melted atglycol, and the like. Where the alcohol corre- I claim: sponds to thealcohol radical of the ester used formoguanamine in the reaction theadditional advantages ob- JACK THEO THURSTON. tained is that noseparation problem results.

The invention will be described in greater de- (References on followingpage) 54.3 parts of hexanoguanamine, which can be prepared by reactionof biguanide with an ester of caproic acid, 43.2 parts ofZ-aminol-methyl thiazole hydrochloride and 20 parts of phenol wereheated together at C. for about 6 hours. 20 The melt was allowed tocool, diluted with water,

made alkaline with concentrated sodium hydroxide solution, thoroughlytriturated, filtered, washed thoroughly with water, and allowed to dry.The guanamine was then recrystallized twice from the ethyl ether ofethylene glycol,

REFERENCES CITED The following references are of record in the file ofthis patent: i gg UNITED STATES PA'IENTS 5 66,096 Number Name Date1,994,602 Wieners Mar. 19, 1935 2,192,127 Ebel Feb. 2'7, 1940 2,217,030Simons Oct. 8, 1 40 2,221,361 Schmid ::Nov.'.12,a1940 2,270,478 SchmidJan. 20, 1942 FOREIGN PATENTS Country Date Switzerland 1924 GreatBritain 1937 Great Britain 1938 'Great Brifiain 1938 OTHER REFERENCESBerichte=der.Deu. Chem., 25, pp. 528, 532, 533.

